Unsaturated derivatives of carbamic acid



UNSATURATED DERIVATIVES OF CABBALHC ACID Albert G. Chenicek, Elmhurst,Long Island, N. Y., assignor to Pittsburgh Plate Glass Company,llttsburgh, Pa a corporation of Pennsylvania.

No Drawing. Application June 25, 1942, Serial No. 448,436

8 Claims. (Cl. 260-78) Thi invention relates to a new class of comratedcarbamate or other amide is dissolved in a pounds which are theN,Nsubstituted bis (unsatsuitable solvent such as benzene, ether,chlorourated alcohol carbamates having the formula: form, toluene,carbon tetrachloride, xylene, and

O petroleum ether, and treated with gaseous phos- H 1B: 5 gene in thepresence of an alkaline agent such as RTOAFNH pyridine or other cyclictertiary amine, or the oxin which R1 is the radical derived from anunsatuides, hydroxides, and carbonates of the alkali rated alcohol, R2is an organic carbonylic radical metals and the alkaline earth metals.The prodto Which the amide ps are attached t o not obtained in solutionmay be washed, dried, and

a carbonyl p 9 the solvent vaporized by heating at reduced pres- I'heunsaturated radicals R1 may be the radisures.

cals derived from alcohols having from three to The new compounds arecapable of polymerizaflve carbon atoms and an unsaturated linkage intion to form solid polymers in the presence of eat.

an aliphatic chain such as allyl, methallyl, 2- alysts such as hydrogenperoxide, oxygen, organic chloroallyl, 2bromoallyl, propargyl,isopropenyl, 5 peroxides, ultraviolet light, heat, etc. The resincrotyl, isocrotyl, chlorocrotyl, ethylallyl, butadiproducts may befabricated by methods wellenyl, tiglyl or angelyl alcohols-methyl vinylcarknown to the prior art. Accordingly, the matebinol, ethyl vinylcarbinol, etc. The radicals may rials may be cast polymerized with orwithout adalso be those derived from unsaturated alcohols mixture ofsuitable solvents to form solid polyhaving six to ten carbon atoms andhaving an unmers of any desirable shape. Compositions may saturatedlinkage in an aliphatic chain such as also be prepared by partiallypolymerizing to a linalool, phenyl propargyl alcohol, cinnamyl alcofusible powder and molding by injection or fusion hol or chlorocinnamylalcohol. under pressure. Such compositions may also con- R2 in the aboveformula, may be any polyvalent tain pigments, fillers, dyes, and/orfibrous reinradicals having terminal carbonyl groups such as 2 forcemenC ng p i ns maybe made by carbonyl, oxalyl, phthalyl, malonyl, succinyl,incorporating in addition solvents and polymerizadipyl, sulphuryl,tricarbellyl, diglycolyl, etc, radlmg a film applied to objects of wood,paper, metal, cals terminated with carbonyl groups such as: or othermaterials.

O O The polymers ma be modified by incorporating u v n 36 plasticizersor by copolymerizing in the presence of butadiene, vinyl chloride, vinylacetate or other 0 o 0 vinyl compounds, phenolic resins, celluloseesters, g g urea plastics, acrylic esters, or similar compounds,unsaturated alcohol esters oi polybasic acids, vinylidene chloride,etc., or with other synthetic CNH-"CQEA'INYHC or natural resins. O 0 OThe nature of the new resins and methods of n H n preparation are morefully set forth in the fol- CI\HCOC:H4-NH-C l i examples:

or Example I Adipyl chloride (5.5 grams) was mixed 6.9 grams ofmethallyl carbamate and heated at '70 The new compounds may generally beprepared to 75 C. until no more hydrogen chloride was y r tin carb matessuch as al yl carbamate, evolved which required about one-half hour. metly Barbamate. 3 1 carba a e, e with The solid product was extracted withhot water d chlorides of D b/ acids such s adipyl and recrystallizedfrom ethyl alcohol. The esterchlolide, phthalyl Chloride,phfisgenesuccinyl amide was a white solid melting at 17a-1'z5 C.chloride, sulphuryl chloride, etc. The reactants Th8 structural f rmulwas f nd to are usually mixed and heated until the hydrogen chloride hasbeen driven off. The product may be leached with water andrecrystallized from a. in 0 43923 suitable solvent. CH8 0 B Whenphosgene is used as the acid chloride a I 1% ll L a specializedtechnique is preferred. The unsatu- J g v acetates Example H 2. Apolymer oi the compound:

Allyl oarbamate (50 g) and 53 grams of phthalyl chloride were heated to7540* c. mfi drogen chloride was evolved for about twenty & H) minutesand the temperature was maintained for ten minutes longer. The solid wasWashed with 1 u hot water and purified by recrystallization from Gib-CHCHPO & NH O benzene. The solid ester-imide was believed to 3 have thestructum: m Apolyler of the compound.

v a w oH, =onon,-o-1-Nn-c=o crn-cn-onPo- -Nn-o-o Example III a Ally! abam t (101 g 35 grams pyri- 4. As anew-compound N,N -bls (carballyloxy)dine, and 500 cc. benzene were placed in a rc- I ph h l having the m arstructure: action flask equipped with a stirring mechanism. The mixturewas cooled in an ice bath -7 and so maintained throughout the reaction.I Phosgene was passed into the flask at the rate of millimoles perminute for one-half hour. 25

\ The excess phosgene was removed by treating V with a small amount ofpyridine and Water. The benzene solution was washed with dilute hydro-CHPQEFCHFO chloric acid then with water. It was dried over NazSO-s andthe benzene evaporated at reduced As a new compound NlNl'bis(carbauymxy) pressures A white solid n 6445 Q) having succinamide havingthe molecular structure:

\ A i H to v 0 H, CH, Q onp-on-onr-o- -nm-c-o Eazumplelv 6. As a newcompound N,N -bis (carbometh- Methany; carbamate 5 grams), 73 grams f mallrloxy) adipamide having the molecular struc. succlnyl chloride and100 cc. of benzene were tum: heated at the reflux temperature for onehour. The benzene and residual HCl was evaporated by heating at reducedpressures." The solid obtained H; I H, was Washed with ethyl alcohol anddried. The I i white crystalline solid was found to correspond 1 I tothe; compound with the'structure: 5 o==c-Nn-c-ocns-cmcn, Ha

H EB CHg J1CH:0g-NH-"-Q 0 E w 7. A compound corresponding to thefollowing oo-nn -ocnson, structural formula; a A five gram sample wasmixed with 1.5 grama v acetone peroxide and heated to 125 C. A brit 0RPO-JL-NH- 2 tle polymer was produced which remained solid attemperatures above 225 C.

Although the invention has been described 7 wherein 1 is a radical c spoi o the rodt respect to mm spegific d t 1g is t ical R1 in the alcoholRrOH, said alcohol bci le intended that these shall be limitations uponthe an unsaturated mvnohydrlc alcohol having from scope of the inventionexcept as incorporated in on three to ten wl'bml atoms and having anall; the f ll wing claims phctic unsaturated'carbon to carbon linkagead- I claim; jaccnt the-beta carbon atom therein and R2 is a L A polymerof the wmpmmd: radical selected from the group consisting of CH9:divalent saturated aliphatic hydrocarbon rada5 ionic and orthophenyleneradical. B. A polymer of the compound defined in OH: I

